WO2015046977A1 - Procédé de fabrication d'un support d'électrode à combustible pour pile à combustible à oxyde solide et support d'électrode à combustible pour pile à combustible à oxyde solide - Google Patents

Procédé de fabrication d'un support d'électrode à combustible pour pile à combustible à oxyde solide et support d'électrode à combustible pour pile à combustible à oxyde solide Download PDF

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WO2015046977A1
WO2015046977A1 PCT/KR2014/009062 KR2014009062W WO2015046977A1 WO 2015046977 A1 WO2015046977 A1 WO 2015046977A1 KR 2014009062 W KR2014009062 W KR 2014009062W WO 2015046977 A1 WO2015046977 A1 WO 2015046977A1
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Prior art keywords
fuel cell
anode support
solid oxide
support
oxide fuel
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PCT/KR2014/009062
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English (en)
Korean (ko)
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허연혁
최광욱
이종진
오탁근
손부원
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주식회사 엘지화학
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Priority to EP14847764.9A priority Critical patent/EP3021396B1/fr
Priority to US14/911,020 priority patent/US10505198B2/en
Priority to CN201480046506.4A priority patent/CN105493328B/zh
Priority to JP2016531557A priority patent/JP6194423B2/ja
Publication of WO2015046977A1 publication Critical patent/WO2015046977A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C11/00—Selection of abrasive materials or additives for abrasive blasts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/801—Sintered carriers
    • H01M4/803—Sintered carriers of only powdered material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present application relates to a method of manufacturing a cathode support of a solid oxide fuel cell and a cathode support of a solid oxide fuel cell.
  • a fuel cell is a device that directly converts chemical energy of fuel and air into electricity and heat by an electrochemical reaction.
  • Fuel cell is a new concept of power generation technology that is not only high in efficiency but also does not cause environmental problems because the existing power generation technology takes combustion of fuel, steam generation, turbine driving, and generator driving.
  • Such a fuel cell has almost no emissions of air pollutants such as SOx and NOx, generates little carbon dioxide, and is a pollution-free power generation. It has advantages such as low noise and no vibration.
  • the medium solid oxide fuel cell has high activation efficiency due to low overvoltage and low irreversible losses based on low activation polarization.
  • PAFC phosphate fuel cell
  • AFC alkaline fuel cell
  • PEMFC polymer electrolyte fuel cell
  • DMFC direct methanol fuel cell
  • SOFC solid oxide fuel cell
  • the medium solid oxide fuel cell (SOFC) has high activation efficiency due to low overvoltage and low irreversible losses based on low activation polarization.
  • it is possible to use not only hydrogen but also carbon or hydrocarbon-based fuels and thus the fuel selection range is wide, and the reaction rate at the electrode is high, thus eliminating the need for expensive precious metals as electrode catalysts.
  • the heat released by the generation is very valuable due to the high temperature.
  • the heat generated from the solid oxide fuel cell is used not only for reforming fuel but also for industrial or cooling energy sources in cogeneration.
  • the solid oxide fuel cell may be classified into a cathode support type, an cathode support type, an electrolyte support type and the like according to the relative thickness of the support.
  • the anode support type SOFC has an advantage that the current resistance is not large even when the anode support has a thick support form due to the high electrical conductivity of the anode.
  • the problem to be solved by the present application is to improve the performance of the fuel cell by improving the interface characteristics between the anode support and the electrolyte of the solid oxide fuel cell to increase the actual area where the hydrogen oxidation reaction occurs in the anode, and the delamination of the interface It is to provide an anode support and a method of manufacturing the same that can prevent the) to improve the durability of the cell.
  • Another object of the present application is to provide a solid oxide fuel cell including the anode support and a manufacturing method thereof.
  • One exemplary embodiment of the present application provides a method of manufacturing a cathode support of a solid oxide fuel cell, comprising surface treating at least one surface of a cathode support including a metal and an inorganic oxide having oxygen ion conductivity by using a blasting method. do.
  • Another embodiment of the present application comprises the steps of preparing a cathode support using the manufacturing method; And applying an inorganic oxide having ion conductivity to the surface-treated surface of the anode support to form an electrolyte.
  • Another exemplary embodiment of the present application provides an anode support of a solid oxide fuel cell manufactured by the manufacturing method.
  • Another embodiment of the present application is a cathode support of a solid oxide fuel cell comprising a metal and an inorganic oxide having oxygen ion conductivity, and at least one surface of the anode support is provided with irregularities of 0.5 micrometer to 10 micrometers in width.
  • the height difference between the highest point and the lowest point of the unevenness provides a fuel cell support of a solid oxide fuel cell, characterized in that 0.1% or more and 50% or less of the total thickness of the anode support.
  • Another embodiment of the present application comprises the steps of preparing the anode support; And applying an inorganic oxide having ion conductivity to the surface-treated surface of the anode support to form an electrolyte.
  • Another embodiment of the present application is the anode support; An air electrode positioned to face the anode support; And it provides a solid oxide fuel cell comprising an electrolyte located between the anode support and the cathode.
  • the anode support of the solid oxide fuel cell may improve the interface characteristics between electrolytes, thereby improving performance of the fuel cell.
  • by preventing delamination of the interface between the anode support and the electrolyte it is possible to slow down the rate at which the efficiency of the fuel cell decreases and to improve the durability of the cell.
  • Example 1 is a graph showing a cross-sectional view of an electrolyte coated on an anode support of Example 1 measured by an electron microscope (SEM).
  • FIG. 2 is a graph illustrating a cross-sectional view of an electrolyte coated on a cathode support of Comparative Example 1 measured by an electron microscope (SEM).
  • FIG. 3 shows data obtained by measuring the surface roughness of the anode support of Example 1 using an optical profiler.
  • One exemplary embodiment of the present application provides a method of manufacturing a cathode support of a solid oxide fuel cell, comprising surface treating at least one surface of a cathode support including a metal and an inorganic oxide having oxygen ion conductivity by using a blasting method. do.
  • the at least one surface means a surface in contact with the electrolyte, and may be part or all of the surface.
  • the surface treated surface may be a portion in contact with the electrolyte.
  • the anode support plays a role of electrochemical oxidation of fuel and electron transfer.
  • the method of manufacturing the anode support may further include reducing the metal oxide to a metal in the anode support including a metal oxide and an inorganic oxide having oxygen ion conductivity.
  • Reduction of the metal oxide may be performed using a conventional method known in the art, and specifically, may be performed in a reducing gas, specifically, a hydrogen gas atmosphere, at a temperature of 550 ° C. or more and 950 ° C. or less.
  • a reducing gas specifically, a hydrogen gas atmosphere
  • the blasting method may be a sand blasting method or a ceramic bead blasting method.
  • the diameter of the sand or ceramic beads may be 0.5 millimeter or more and 10 millimeters or less. It should be 0.5 millimeter or more to allow the surface treatment of the anode support to be possible, and 10 millimeters or less to prevent a problem that may significantly weaken the strength of the anode support when the diameter is large.
  • the types of ceramic beads are gadolinium doped ceria (GDC), gadolinium doped zirconia (GDZ), samarium doped ceria (SDC), samarium doped zirconia (SDZ), yttrium doped ceria (YDC) And yttrium-doped zirconia (YDZ), yttria stabilized zirconia (YSZ) and scandia stabilized zirconia (ScSZ).
  • GDC gadolinium doped ceria
  • GDZ gadolinium doped zirconia
  • SDC samarium doped ceria
  • SDZ samarium doped zirconia
  • YDC yttrium doped ceria
  • YDZ yttrium-doped zirconia
  • YSZ yttria stabilized zirconia
  • ScSZ scandia stabilized zirconia
  • the injection speed in the blast method is not particularly limited, but may be in a range of 0.1 m / sec or more and 41.6 m / sec or less.
  • the surface treatment of the anode support may be performed at 0.1 m / sec or more, and when the blast speed is excessively large at 41.6 m / sec or less, a problem that may significantly weaken the strength of the anode support may be prevented.
  • the injection pressure in the blast method is not particularly limited, but may be 0.5 bar or more and 5 bar or less.
  • the metal is one selected from the group consisting of Zr, Ce, Ti, Mg, Al, Si, Mn, Fe, Co, Ni, Cu, Zn, Mo, Y, Nb, Sn, La, Ta, V and Nd or There may be more than one.
  • Ni can be used.
  • Ni has high electronic conductivity and at the same time, adsorption of hydrogen and a hydrocarbon-based fuel occurs, thereby exhibiting high electrode catalyst activity.
  • the inorganic oxide having oxygen ion conductivity is gadolinium-doped ceria (GDC), gadolinium-doped zirconia (GDZ), samarium-doped ceria (SDC), samarium-doped zirconia (SDZ), yttrium-doped ceria (YDC), yttrium doped zirconia (YDZ), yttria stabilized zirconia (YSZ) and scandia stabilized zirconia (ScSZ).
  • GDC gadolinium doped ceria
  • GDZ gadolinium-doped zirconia
  • SDC samarium-doped ceria
  • SDZ samarium-doped zirconia
  • YDC yttrium-doped ceria
  • YDZ yttrium doped zirconia
  • YSZ yttria stabilized zir
  • the surface-treated surface may include irregularities having a width of 0.5 micrometers or more and 10 micrometers or less, and the height difference between the highest and lowest points of the irregularities may be 0.1% or more and 50% or less of the total thickness of the anode support.
  • the width of the concavities and convexities may be adjusted according to the size (eg, the diameter of the sphere in the case of a sphere) that is sprayed using the blast method. The larger the particles to be sprayed, the larger the unevenness of the width tends to be.
  • the width and depth of the concavities and convexities may be measured by an optical profiler, and more precisely, may be measured by photographing a cross section with an electron microscope (SEM).
  • the width means a distance from the lowest point of any one concave portion to the lowest point of the adjacent concave portion in the cross section of the concave-convex.
  • adjacent yaw parts means two yaw parts having an iron part therebetween. That is, the width of the unevenness means a straight line distance between the floor and the floor or the valley and the valley when the unevenness is viewed from the top surface, and the height difference between the highest and lowest points of the unevenness is from the surface including the deepest floor to the highest point. Means vertical distance. Referring to FIG. 1, A denotes a width of unevenness, and may be measured as a straight distance between the floor and the floor in the top view of the unevenness formed on the anode support.
  • the height difference between the highest point and the lowest point of the unevenness may mean a vertical distance from the surface including the lowest point of the unevenness to the highest point of the unevenness.
  • the depth indicated by B represents the vertical distance between the floors of the uneven surface having the highest point in the plane including the low point of any unevenness at the position measured in FIG. 1.
  • the vertical distance from the surface having the lowest valley among the unevenness in the entire anode support, that is, including the lowest point of the unevenness, that is, the vertical distance from the highest point of the unevenness will be the difference between the heights of the highest and lowest points of the unevenness.
  • the height difference between the highest point and the lowest point of the unevenness may mean a difference between the lowest point and the highest point of the surface-treated surface.
  • the surface area of the support can be increased by 1.5 times or more and 10 times or less as compared with the case where the blast surface treatment is not performed when the anode support is manufactured.
  • the surface area of the surface treated surface may increase by 1.5 times or more and 10 times or less than the surface area before the surface treatment.
  • TPB triple phase boundary
  • the performance of the fuel cell is improved. It also has the effect of preventing foliar phenomenon at the interface.
  • the roughness of the surface treated surface may be greater than or equal to 150 nanometers and less than or equal to 900 nanometers. If it is 150 nanometers or more, the surface treatment effect is excellent, and if it is 900 nanometers or less, the problem which may be destroyed by the crack of an anode support during operation at high temperature can be prevented.
  • the roughness means Arithmetical average roughness (Ra).
  • the center line average roughness is obtained by averaging the height and depth of the hill and valley within the reference length with respect to the center line, and means a distance from the center line.
  • the center line is a straight line in which the area surrounded by the straight line and the cross-sectional curve becomes equal when a straight line parallel to the average cross-sectional curve is drawn within the reference length.
  • the surface roughness may be measured by any method as long as it is known in the art, and may be measured using, for example, an optical profiler.
  • the area specific resistance (ASR) of the surface-treated surface may be 0.01 cm 2 or more and 0.45 mm 2 or less. At this time, the area specific resistance can be measured by any method known in the art, for example, can be measured by a high temperature impedance method.
  • the area resistivity (ARS) is an alternating current impedance characteristic of the electrolyte and the electrode interface, and the lower the value, the lower the resistance of the interface between the electrolyte and the electrode. According to an exemplary embodiment of the present application, the area of the interface is increased by the surface treatment to increase the place where it can react, and accordingly, the sheet resistance (area specific resistance) is lowered within the range, thereby improving the performance of the fuel cell. have.
  • the thickness of the anode support may be usually 0.5 millimeter or more and 50 millimeters or less. More specifically, it may be 1 millimeter or more and 10 millimeters or less. When in the above range, it is possible to maintain the physical strength to indicate the stability of the fuel cell, and to exhibit high fuel cell performance with low electrical resistance.
  • the above-described materials of the anode support may be used singly or in combination of two or more kinds, the anode support may be formed alone, or an additional anode may be further formed on the anode support.
  • the anode of the multilayer structure may be further formed by using different anode materials.
  • the anode support may use coarse particles of several micrometers or more as a starting metal and an inorganic oxide having oxygen ion conductivity to delay densification of the anode support during sintering.
  • the triple phase boundary (TPB) may not be sufficiently formed inside the anode after sintering, so that the functional layer (FL) having the same composition as the anode support and the particle size is fine between the anode support and the electrolyte.
  • Functional Layer may be further included.
  • One exemplary embodiment of the present application provides an anode support of a solid oxide fuel cell manufactured by the above manufacturing method.
  • One embodiment of the present application comprises the steps of preparing a cathode support using the manufacturing method; And applying an inorganic oxide having ion conductivity to the surface-treated surface of the anode support to form an electrolyte.
  • the inorganic oxide included in the electrolyte may be the same as the inorganic oxide included in the anode support.
  • the electrolyte must be dense so that air and fuel are not mixed, and have high oxygen ion conductivity and low electron conductivity.
  • the fuel electrode and the air electrode having a very large oxygen partial pressure difference are located at both sides of the electrolyte, it is necessary to maintain the above physical properties in a wide oxygen partial pressure region.
  • the inorganic oxide included in the electrolyte is not particularly limited as long as it can be generally used in the art, for example, zirconia-based doped or not doped with at least one of gadolinium, yttrium, samarium, scandium, calcium and magnesium; Ceria based or not doped with at least one of gadolinium, samarium, lanthanum, ytterbium and neodymium; Bismuth oxide based or doped with at least one of calcium, strontium, barium, gadolithium and yttrium; And a lanthanum gallate system doped or undoped with at least one of strontium and magnesium.
  • GDC gadolinium doped ceria
  • GDZ gadolinium doped zirconia
  • SDC samarium doped ceria
  • SDZ samarium doped zirconia
  • YDC yttrium doped ceria
  • YDZ doped zirconia
  • YSZ yttria stabilized zirconia
  • ScSZ scandia stabilized zirconia
  • the thickness of the electrolyte may be usually 10 nanometers or more and 100 micrometers or less. More specifically, the thickness may be 100 nanometers or more and 50 micrometers or less.
  • the method of forming an electrolyte on the anode support may use a vacuum deposition method such as a typical slurry coating method including a dip-coating, painting, etc., a tape casting method, a screen printing method, a wet spray method or a chemical vapor deposition method, and a physical vapor deposition method.
  • a vacuum deposition method such as a typical slurry coating method including a dip-coating, painting, etc., a tape casting method, a screen printing method, a wet spray method or a chemical vapor deposition method, and a physical vapor deposition method.
  • the electrolyte may be sintered by heat treatment.
  • the heat treatment temperature may be 800 ° C or more and 1,500 ° C or less.
  • the method of manufacturing a solid oxide fuel cell may further include forming an cathode by applying an anode composition to an electrolyte.
  • the fuel cell cathode refers to a layer in which an electrochemical reaction takes place by an oxygen reduction catalyst in a fuel cell. Oxygen gas is reduced to oxygen ions, and air is kept flowing to the cathode to maintain a constant oxygen partial pressure.
  • metal oxide particles having a perovskite type crystal structure may be used.
  • LSM lanthanum-strontium manganese oxide
  • LSF lanthanum-strontium iron oxide
  • BSCF barium-strontium cobalt iron oxide
  • bismuth-ruthenium oxide Compound any one or more selected from the group consisting of oxide (LSC), lanthanum-strontium cobalt iron oxide (LSCF), samarium-strontium cobalt oxide (SSC), barium-strontium cobalt iron oxide (BSCF) and bismuth-ruthenium oxide Compound.
  • the material for forming the cathode layer it is also possible to use precious metals such as platinum, ruthenium and palladium.
  • the above-mentioned cathode materials may be used alone or in combination of two or more thereof. It is possible to form a cathode of a multilayer structure using a cathode of a single layer structure or different cathode materials.
  • the cathode composition may further include an inorganic oxide, a binder resin, and a solvent having oxygen ion conductivity.
  • the binder resin is not limited as long as it is a binder resin capable of imparting adhesion, and may be, for example, ethyl cellulose.
  • the solvent is not limited as long as it can dissolve the binder resin, and may be any one or two or more kinds selected from the group consisting of butyl carbitol, terpineol and butyl carbitol acetate.
  • the cathode composition may be sintered by heat treatment.
  • the heat treatment temperature may be 800 ° C. or more and 1,200 ° C. or less.
  • the oxygen reduction catalyst may be sintered together with the inorganic oxide, and below 1,200 ° C, the oxygen reduction catalyst may be sintered without reacting with the electrolyte.
  • the thickness of the air electrode may be usually 1 micrometer or more and 100 micrometers or less. More specifically, the thickness may be 5 micrometers or more and 50 micrometers or less.
  • the method of forming an air electrode in the electrolyte may be a tape casting method, a screen printing method, or a wet spray method.
  • a functional layer may be further included between the cathode and the electrolyte as necessary to more effectively prevent a reaction therebetween.
  • Such functional layers may include, for example, one or more selected from the group consisting of gadolinium doped ceria (GDC), samarium doped ceria (SDC) and yttrium doped ceria (YDC).
  • GDC gadolinium doped ceria
  • SDC samarium doped ceria
  • YDC yttrium doped ceria
  • the functional layer may have a thickness in a range of 1 micrometer or more and 50 micrometers or less, for example, 2 micrometers or more and 10 micrometers or less.
  • One exemplary embodiment of the present application is a cathode support of a solid oxide fuel cell including a metal and an inorganic oxide having oxygen ion conductivity, and at least one surface of the anode support includes irregularities having a width of 0.5 micrometers or more and 10 micrometers or less. The height difference between the highest point and the lowest point of the unevenness provides the anode support of the solid oxide fuel cell having 0.1% or more and 50% or less of the total thickness of the anode support.
  • the roughness of the surface of the anode support provided with the unevenness may be 150 nm or more and 900 nm or less.
  • An area specific resistance (ASR) of the surface of the anode support provided with the unevenness may be 0.01 ⁇ cm 2 or more and 0.45 ⁇ cm 2 or less.
  • the surface of the anode support provided with the unevenness is a portion in contact with the electrolyte.
  • One embodiment of the present application comprises the steps of preparing the anode support; And applying an inorganic oxide having ion conductivity to the surface-treated surface of the anode support to form an electrolyte.
  • One embodiment of the present application is the anode support; An air electrode positioned to face the anode support; And it provides a solid oxide fuel cell comprising an electrolyte located between the anode support and the cathode.
  • the solid oxide fuel cell can be manufactured using conventional methods known in various literatures in the art.
  • the solid oxide fuel cell may be applied to various structures, such as a cylindrical stack, a flat tubular stack, and a planar type stack.
  • a cathode support having a thickness of 3 millimeters was prepared by a one-axis pressurization method and sintered at a temperature of 1450 ° C. using a 50:50 volume ratio of GDC (10 mole% Gd doped Ceria) and NiO as the anode support. Thereafter, NiO / GDC was reduced to Ni / GDC for 30 minutes using reducing gas (H 2 ) at a temperature of 850 ° C.
  • Unevenness of 1 micrometer in width was formed on the surface treated with the blast method, and the height difference between the highest and lowest points of the unevenness was 20 micrometers. At this time, the roughness of the surface was 300 nanometers as measured using an optical profiler. The area specific resistance of the surface was 0.3 ⁇ cm 2 as measured by the AC impedance method.
  • the surface roughness of the anode support of Example 1 was measured using an optical profiler, and the data is shown in FIG. 3.
  • FIG. 3 is a top view of an anode support including irregularities measured by an optical profiler. It can be seen that the deeper the red, the deeper the valleys of the unevenness. The blue the higher the level of the unevenness. The blue color near zero is the lowest of the measured points, that is, the lowest point of unevenness.
  • the portion a shown in FIG. 3 is blue, and it can be seen that it is a low position on the surface of the anode support, the portion c can be seen that it is a high position on the surface of the anode support, and the portion b is an intermediate position of the surface of the anode support. Able to know. It can be confirmed that there is an unevenness according to the color change shown in FIG. 3, the width or depth of the unevenness can be roughly measured, and the roughness measured by the optical profiler can be confirmed.
  • Ra means a center line average roughness
  • Rq means a square mean roughness, and can be obtained by using a root mean square (rms) method.
  • Rt means distance between the highest and the lowest point of the profile within the average length Lm (Evalution Length).
  • Rz is a ten point median height, which means a difference between the average height of the five highest mountains and the average depth of the deepest valleys in the cross-sectional curve.
  • a cross-sectional view of the electrolyte applied on the surface-treated surface of the anode support of Example 1 was taken in an electron microscope (SEM) and is shown in FIG. 1. It can be confirmed that there is irregularities in the graph of FIG. 1, and the width A and the depth B of the irregularities can be measured in detail.
  • the width of the unevenness means a straight line distance between the floor and the floor or the valley and the valley when the unevenness is viewed from the top surface, and the height difference between the highest and lowest points of the unevenness includes the deepest floor. Means the vertical distance from the surface to the highest point.
  • A denotes a width of unevenness, and may be measured as a straight distance between the floor and the floor in the top view of the unevenness formed on the anode support.
  • the depth indicated by B represents the vertical distance between the floors of the uneven surface having the highest point in the plane including the low point of any unevenness at the position measured in FIG. 1.
  • One millimeter diameter ceria beads were treated on one surface of the Ni / GDC anode support prepared in Example 1 by blasting for 10 minutes at a speed of 40 m / sec at a pressure of 5 bar.
  • Unevenness of 0.5 micrometers in width was formed on the surface treated with the blast method, and the height difference between the highest and lowest points of the unevenness was 20 micrometers.
  • the surface roughness was 500 nanometers when measured using an optical profiler, and the surface area resistivity was 0.3 0.3cm 2 when measured by an alternating current impedance method.
  • a cross-sectional view of the electrolyte coated on the anode support of Comparative Example 1 was taken in an electron microscope (SEM) and is shown in FIG. 2.
  • GDC was applied to the surface of the anode support prepared in Example 1 by a dip coating method to a thickness of 10 micrometers and sintered at a temperature of 1450 ° C to form an electrolyte.
  • LSCF was applied on the electrolyte to a thickness of 30 micrometers by screen printing, followed by sintering at a temperature of 1000 ° C. to form an air cathode layer, thereby preparing a fuel cell.
  • a fuel cell was manufactured in the same manner as in Example 1 using the anode support of Example 2.
  • a fuel cell was manufactured using the anode support of Comparative Example 1 in the same manner as in Preparation Example 1.

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Abstract

La présente invention concerne un procédé de fabrication d'un support d'électrode à combustible destiné à une pile à combustible à oxyde solide, ainsi qu'un support d'électrode à combustible pour pile à combustible à oxyde solide, qui améliorent une propriété interfaciale entre le support d'électrode à combustible et un électrolyte, améliorant ainsi les performances et la durabilité de la pile à combustible.
PCT/KR2014/009062 2013-09-27 2014-09-26 Procédé de fabrication d'un support d'électrode à combustible pour pile à combustible à oxyde solide et support d'électrode à combustible pour pile à combustible à oxyde solide WO2015046977A1 (fr)

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EP14847764.9A EP3021396B1 (fr) 2013-09-27 2014-09-26 Procédé de fabrication d'un support d'électrode à combustible pour pile à combustible à oxyde solide et support d'électrode à combustible pour pile à combustible à oxyde solide
US14/911,020 US10505198B2 (en) 2013-09-27 2014-09-26 Method for manufacturing fuel electrode support for solid oxide fuel cell and fuel electrode support for solid oxide fuel cell
CN201480046506.4A CN105493328B (zh) 2013-09-27 2014-09-26 制造固体氧化物燃料电池的燃料电极支撑体的方法和固体氧化物燃料电池的燃料电极支撑体
JP2016531557A JP6194423B2 (ja) 2013-09-27 2014-09-26 固体酸化物燃料電池の燃料極支持体の製造方法

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KR20150035457A (ko) 2015-04-06
US10505198B2 (en) 2019-12-10
JP6194423B2 (ja) 2017-09-06
EP3021396A4 (fr) 2017-01-25
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US20160197355A1 (en) 2016-07-07
EP3021396A1 (fr) 2016-05-18

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